Diarylbutadiene-substituted methyltrialkylsilanes and photoprotective compositions comprised therof

ABSTRACT

Novel 4,4-diarylbutadiene-substituted methyltrialkylsilanes having the structural formula (I):  
                 
are useful sunscreens for UV-photoprotecting human skin against the damaging effects of UV-radiation, notably UV-A radiation.

CROSS-REFERENCE TO PRIORITY/PROVISIONAL APPLICATIONS

This application claims priority under 35 U.S.C. § 119 of FR 03/50899,filed Nov. 25, 2003, and of provisional application Ser. No. 60/526,988,filed Dec. 5, 2003, each hereby expressly incorporated by reference andeach assigned to the assignee hereof. This application is also acontinuation of said '988 provisional.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

The present invention relates to novel methyltrialkylsilanes containinga 4,4-diarylbutadiene functional group.

The present invention also relates to the formulation of thesemethyltrialkylsilanes containing a 4,4-diarylbutadiene function intocosmetic or dermatological compositions useful for screening out UVradiation having wavelengths of from 320 to 400 nm.

This invention also relates to cosmetic or dermatologicalphotoprotective compositions containing at least one 4,4-diarylbutadienefunctionalized methyltrialkylsilane, formulated into a cosmeticallyacceptable vehicle therefor.

2. Description of Background and/or Related and/or Prior Art

It is known that radiation with wavelengths of between 280 nm and 400 nmpermits tanning of the human epidermis and that radiation withwavelengths of between 280 and 320 nm, which is known as UV-B radiation,causes skin burns and erythema that may be harmful to the development ofa natural tan. For these reasons and also for aesthetic reasons, thereis increasing demand for means for controlling this natural tanning.This UV-B radiation should thus be screened out.

It is also known that UV-A rays, with wavelengths of between 320 and 400nm, which cause browning of the skin, are liable to induce impairment inthe skin, especially in the case of sensitive skin and/or skin that iscontinually exposed to sunlight. UV-A rays in particular result in aloss of elasticity of the skin and the appearance of wrinkles, leadingto premature aging of the skin. They promote triggering of the erythemalreaction or amplify this reaction in the case of certain individuals andmay even be the cause of phototoxic or photoallergic reactions. Thus,for aesthetic and cosmetic reasons such as the conservation of thenatural elasticity of the skin, more and more individuals wish tocontrol the effect of UV-A rays on their skin. It is thus desirable alsoto screen out UV-A radiation.

There is at the present time an ever-increasing need for aromaticcompounds that are effective at screening out UV-A radiation andpreferably in the range from 340 to 400 nm (range known as long UV-A orUV-A-1). Besides their good photoprotective efficacy in this range, thedesired UV-A screening agents should have good cosmetic properties, goodsolubility in the usual solvents and in particular in fatty substancessuch as oils and fats, good resistance to water and to perspiration(remanence) and also satisfactory photostability.

A limited number of organic compounds that are effective towards UV-Arays and especially long UV-A rays are currently available on theUV-screening agent market.

In this regard, one family of UV-A screening agents that is particularlyeffective in the UV-A range currently includes dibenzoylmethanederivatives, and especially 4-tert-butyl-4′-methoxydibenzoylmethane,which specifically have good intrinsic absorbing power. Thesedibenzoylmethane derivatives, which are now products that are well knownper se as screening agents active in the UV-A range, are describedespecially in FR-A-2,326,405 and FR-A-2,440,933, and also inEP-A-0-114,607; 4-tert-butyl-4′-methoxydibenzoylmethane is moreovercurrently sold under the trademark “Parsol 1789” by Hoffmann LaRoche.

Unfortunately, it transpires that dibenzoylmethane derivatives areproducts that are relatively photosensitive to UV-A radiation, i.e.,more specifically, they have an annoying tendency to be degraded more orless quickly by the action of this radiation. Thus, this substantiallack of photochemical stability of dibenzoylmethane derivatives withrespect to ultraviolet radiation, to which they are by nature intendedto be subjected, does not make it possible to ensure constant protectionduring prolonged exposure to the sun, and as a result the user needs tomake repeated applications at regular and short intervals in order toobtain effective protection of the skin against UV rays.

Another difficulty, which is independent of the one mentioned above,encountered with dibenzoylmethane derivatives is that they arelipophilic screening agents that have the particular feature but alsothe drawback of being solid at room temperature. As a result, their usein an antisun or sunscreen cosmetic composition entails certainconstraints as regards their formulation and application, in particularwhen it is a matter of finding solvents for dissolving them correctly,alone or in combination with other screening agents.

Thus, need continues to exist for novel families of aromatic compoundsthat are effective in terms of screening in the UV-A range andespecially the long UV-A range, but which are photostable and also haveboth good solubility in the usual solvents and good cosmetic properties,and also good resistance to water and to perspiration (remanence).

SUMMARY OF THE INVENTION

Surprisingly, a novel family of methyltrialkylsilanes containing a4,4-diarylbutadiene functional group has now been developed whichameliorates or avoids the above disadvantages and drawbacks of the priorart.

The present invention thus features a novel family ofmethyltrialkylsilanes containing a 4,4-diarylbutadiene function ofgeneral formula (1) more fully described hereinbelow.

This invention also features the formulation of at least onemethyltrialkylsilane containing a 4,4-diarylbutadiene function ofgeneral formula (1) into cosmetic or dermatological compositions usefulfor screening out UV rays with wavelengths of from 320 to 400 nm.

The present invention accordingly features photoprotective compositionscomprising at least one methyltrialkylsilane containing a4,4-diarylbutadiene function.

The present invention also features cosmetic or dermatologicalphotoprotective compositions, comprising, formulated into a cosmeticallyacceptable support, at least one methyltrialkylsilane containing a4,4-diarylbutadiene function of general formula (1) more fully describedhereinbelow.

The methyltrialkylsilanes containing a 4,4-diarylbutadiene functionalgroup in accordance with the invention, are in isolated form or in theform of a mixture and correspond to the general formula (1) below:

in which the radicals R₁, which may be identical or different, are eacha hydroxyl group, a saturated or unsaturated, linear or branched C₁-C₁₀alkyl radical, a linear or branched C₁-C₁₀ alkoxy radical, with theproviso that two adjacent groups R₁ may together form a C₁-C₃alkylenedioxy ring; the radicals R₂, R₃ and R₄, which may be identicalor different, are each a saturated or unsaturated, linear or branchedC₁-C₁₀ alkyl radical optionally containing one or more halogen atoms(for example Cl, Br, F), or a phenyl radical; p is 0 or 1; A is ahydrogen atom, a saturated or unsaturated, linear or branched C₁-C₈alkyl radical, a phenyl radical, or the group Si(CH₃)₃, with the provisothat, if A is Si(CH₃)₃, then p=0 and R₂, R₃ and R₄ are methyl radicals;n is an integer ranging from 0 to 2; W is a saturated or unsaturated,linear or branched C₁-C₈ alkylene radical optionally substituted by ahydroxyl group; Z is a hydrogen atom, —(C═O)OR₅, —(C═O)R₆, —(C═O)NR₇R₈,—SO₂R₉, —CN or —(C═O)XCHA(W)_(p)SiR₂R₃R₄; the radical R₅ is a hydrogenatom, or a saturated or unsaturated, linear or branched C₁-C₂₀ alkylradical; the radical R₆ is a linear or branched, optionally cyclic,C₁-C₂₀ alkyl radical or a C₆-C₁₂ aryl radical; the radicals R₇ and R₈,which may be identical or different, are each a hydrogen atom or alinear or branched C₁-C₂₀ alkyl radicals; X is —O— or —NR₇—; and theradical R₉ is a linear or branched C₁-C₂₀ alkyl radical or a C₆-C₁₂ arylradical.

DETAILED DESCRIPTION OF BEST MODE AND SPECIFIC/PREFERRED EMBODIMENTS OFTHE INVENTION

Although, in formula (1) above, only the isomers in which thesubstituent Z is in the cis position relative to the diaryl substituentare represented, this formula should be understood as also including thecorresponding trans isomer.

In formula (1) above, the alkyl radicals may be linear or branched,saturated or unsaturated and selected especially from among methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl,isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl andtert-octyl radicals. The alkyl radical that is particularly preferred isthe methyl radical.

In formula (1) above, the alkoxy radicals may be linear or branched andselected especially from among methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy and isobutoxy radicals. The alkoxy radical that is particularlypreferred is the methoxy radical.

In formula (1) above, the aryl radicals are preferably phenyl.

The methyltrialkylsilanes containing a 4,4-diarylbutadiene function offormula (1) preferably satisfy at least one, and even more preferablyall, of the following characteristics:

Z=—(C═O)OR₅, —CN or (C═O)XCHA(W)_(n)SiR₂R₃R₄;

R₅ is methyl or ethyl;

A is H;

R₂ to R₄ are C₁-C₄ alkyl radicals and more preferably methyl;

n is 0;

p is 0 or 1; and

W is a C₁-C₂ alkylene radical.

Among the preferred methyltrialkylsilanes containing a4,4-diarylbutadiene function of formula (1), the compounds (A), (B) and(C) having the following formulae are representative:

One family of methyltrialkylsilanes containing a 4,4-diarylbutadienefunction of formula (1) that are particularly preferred are those inwhich Z is —CN. These particular compounds are effective in the range oflong UV-A rays (340-400 nm).

Among these compounds, the ones that are preferred are those satisfyingat least one of the following characteristics and even more preferablyall of the following characteristics:

A is H;

R₂ to R₄ are C₁-C₄ alkyl radicals and more preferably methyl;

n is 0;

p is 0 or 1, and

W is a C₁-C₂ alkylene radical.

Among these compounds, even more particularly preferred are thecompounds (D), (E), (F) and (G) below:

The silane derivatives of formula (1) are obtained by Knoevenagelcondensation of a β-phenylcinnamaldehyde derivative of formula (2) on aderivative with activated methylene of formula (3) as described inEP-O-916,335 according to Scheme (1) below:

in which the radicals R₁ to R₄, Z, X, A, W, n and p have the samemeaning as in formula (1).

The derivatives of formula (3) can be obtained by one of the threeroutes described in Scheme (2) below:

in which Z, A, W, R₂ to R₄, R₇ and p have the same meanings as thoseindicated above for the formula (1), Hal represents a halogen and moreparticularly chlorine and M⁺ represents an alkali metal and moreparticularly sodium or potassium.

As derivatives of formula (4), mention may be made of cyanoacetic acid,monoethyl malonate (RN 1070-46-1) or mono-tert-butyl malonate, which arecommercial products.

As derivatives of formula (5), mention may be made ofhydroxymethyltrimethylsilane (RN 3219-63-4) or 2-(trimethylsilyl)ethanol(RN 2916-68-9), which are commercial products.

As derivatives of formula (6), mention may be made of potassiummonoethyl malonate (RN 6148-64-7), which is a commercial product.

As silane halide derivatives of formula (7), mention may be made ofchloropropyltrimethylsilane (RN 2344-83-4) orchloromethyltrimethylsilane (RN 2344-80-1), which is sold by Wacker.

Mention may also be made of the following commercial products:iodomethyltrimethylsilane (RN 4206-67-1),(chloromethyl)dimethylethylsilane (RN 3121-77-5),(chloromethyl)dimethyl-n-butylsilane (RN 3121-75-3),(chloromethyl)dimethylpentylsilane (RN 73013-39-5),(chloromethyl)dodecyidimethylsilane (RN 7085147-7),(chloromethyl)triethylsilane (RN 757-34-6), 2-chloroethyltrimethylsilane(RN 7787-87-3), bis(trimethylsilyl)methyl chloride (RN 5926-35-2),(chloromethyl)dimethylphenylsilane (RN 1833-51-8),(chloromethyl)diphenylmethylsilane (RN 1840740-4) and(trimethylsilylmethyl)dimethylchloromethylsilane (RN 18306-73-5).

As a derivative of formula (8), mention may be made of hydrogenmonoethyl malonate chloride or malonyl dichloride, which are commercialproducts.

As derivatives of formula (9), mention may be made ofaminomethyltrimethylsilane (RN 18166-02-4), sold by Gelest, and(phenyl)(trimethylsilyl)methylamine or bis(trimethylsilyl)methylamine(RN 134340-00-4).

The compounds of formula (I) are generally present in the compositionsof the invention in proportions of between 0.01% and 20% by weight andpreferably between 0.1% and 10% by weight relative to the total weightof the composition.

The compositions in accordance with the invention may also compriseother additional UV-A-active and/or UV-B-active organic or mineralUV-screening agents that are water-soluble, liposoluble or eveninsoluble in the cosmetic solvents commonly used.

The additional organic screening agents are selected especially fromamong the anthranilates; cinnamic derivatives; dibenzoylmethanederivatives; salicylic derivatives; camphor derivatives; triazinederivatives such as those described in U.S. Pat. No. 4,367,390,EP-863,145, EP-517,104, EP-570,838, EP-796,851, EP-775,698, EP-878,469,EP-933,376, EP-507,691, EP-507,692, EP-790,243, EP-944,624; benzophenonederivatives; β,β-diphenylacrylate derivatives; benzotriazolederivatives; benzalmalonate derivatives; benzimidazole derivatives;imidazolines; bis-benzazolyl derivatives as described in EP-669,323 andU.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives;methylenebis(hydroxyphenylbenzotriazole) derivatives as described inU.S. Pat. Nos. 5,237,071, 5,166,355, GB-2,303,549, DE-197,26 184 andEP-893,119; benzoxazole derivatives as described in EP-0-832,642,EP-1-027,883, EP-1-300,137 and DE-101,62,844; screening polymers andscreening silicones such as those described especially in WO 93/04665;α-alkylstyrene-based dimers, such as those described in DE-198,55,649;non-siliceous 4,4-diarylbutadienes such as those described inEP-0-967,200, DE-197,46,654, DE-197,55,649, EP-A-1-008,586, EP-1-133,980and EP-133,981, and mixtures thereof.

As examples of additional organic screening agents, mention may be madeof those denoted hereinbelow under their INCI name:

Para-Aminobenzoic Acid Derivatives:

PABA,

Ethyl PABA,

Ethyl dihydroxypropyl PABA,

Ethylhexyl dimethyl PABA sold in particular under the name “Escalol 507”by ISP,

Glyceryl PABA,

PEG-25 PABA sold under the name “Uvinul P25” by BASF.

Salicylic Derivatives:

Homosalate sold under the name “Eusolex HMS” by Rona/EM Industries,Ethylhexyl salicylate sold under the name “Neo Heliopan OS” by Haarmannand Reimer,

Dipropylene glycol salicylate sold under the name “Dipsal” by Scher, TEAsalicylate sold under the name “Neo Heliopan TS” by Haarmann and Reimer.

Dibenzoylmethane Derivatives:

Butyl methoxydibenzoylmethane sold in particular under the trademark“Parsol 1789” by Hoffmann LaRoche,

Isopropyldibenzoylmethane.

Cinnamic Derivatives:

Ethylhexyl methoxycinnamate sold in particular under the trademark“Parsol MCX” by Hoffmann LaRoche,

Isopropyl methoxycinnamate,

Isoamyl methoxycinnamate sold under the trademark “Neo Heliopan E 1000”by Haarmann and Reimer,

Cinoxate,

DEA methoxycinnamate,

Diisopropyl methylcinnamate,

Glyceryl ethylhexanoate dimethoxycinnamate.

β,β′-Diphenylacrylate Derivatives:

Octocrylene sold in particular under the trademark “Uvinul N539” byBASF,

Etocrylene sold in particular under the trademark “Uvinul N35” by BASF.

Benzophenone Derivatives:

Benzophenone-1 sold under the trademark “Uvinul 400” by BASF,

Benzophenone-2 sold under the trademark “Uvinul D50” by BASF,

Benzophenone-3 or Oxybenzone sold under the trademark “Uvinul M40” byBASF,

Benzophenone-4 sold under the trademark “Uvinul MS40” by BASF,

Benzophenone-5,

Benzophenone-6 sold under the trademark “Helisorb 11” by Norquay,

Benzophenone-8 sold under the trademark “Spectra-Sorb UV-24” by AmericanCyanamid,

Benzophenone-9 sold under the trademark “Uvinul DS-49” by BASF,Benzophenone-12,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate.

Benzylidenecamphor Derivatives:

3-Benzylidenecamphor manufactured under the name “Mexoryl SD” by Chimex,

4-Methylbenzylidenecamphor sold under the name “Eusolex 6300” by Merck,

Benzylidenecamphorsulfonic acid manufactured under the name “Mexoryl SL”by Chimex,

Camphor benzalkonium methosulfate manufactured under the name “MexorylSO” by Chimex,

Terephthalylidenedicamphorsulfonic acid manufactured under the name“Mexoryl SX” by Chimex,

Polyacrylamidomethylbenzylidenecamphor manufactured under the name“Mexoryl SW” by Chimex.

Phenylbenzimidazole Derivatives:

Phenylbenzimidazolesulfonic acid sold in particular under the trademark“Eusolex 232” by Merck,

Disodium phenyl dibenzimidazole tetrasulfonate sold under the trademark“Neo Heliopan AP” by Haarmann and Reimer.

Triazine Derivatives:

Anisotriazine sold under the trademark “Tinosorb S” by Ciba Geigy,

Ethylhexyltriazone sold in particular under the trademark “Uvinul T150”by BASF,

Diethylhexylbutamidotriazone sold under the trademark “UV-Asorb HEB” bySigma 3V.

Phenylbenzotriazole Derivatives:

Drometrizole trisiloxane sold under the name “Silatrizole” by RhodiaChimie,

Methylenebis(benzotriazolyl)tetramethylbutylphenol sold in solid formunder the trademark “Mixxim BB/100” by Fairmount Chemical, or inmicronized form as an aqueous dispersion under the trademark “TinosorbM” by Ciba Specialty Chemicals.

Anthranilic Derivatives:

Menthyl anthranilate sold under the trademark “Neo Heliopan MA” byHaarmann and Reimer.

Imidazoline Derivatives:

Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate Derivatives:

Polyorganosiloxane containing a benzalmalonate function, such as theproduct Polysilicone-15 sold under the trademark “Parsol SLX” byHoffmann LaRoche.

Non-Siliceous 4,4-diarylbutadiene Derivatives:

1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene.

Benzoxazole Derivatives:

2,4-Bis[5-1(dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazinesold under the name UV-Asorb K2A by Sigma 3V,

and mixtures thereof.

The additional organic UV-screening agents that are preferred are:

Ethylhexyl salicylate,

Ethylhexyl methoxycinnamate,

Butyl methoxydibenzoylmethane,

Octocrylene,

Phenylbenzimidazolesulfonic acid,

Benzophenone-3,

Benzophenone-4,

Benzophenone-5,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,

4-Methylbenzylidenecamphor,

Terephthalylidenedicamphorsulfonic acid,

Disodium phenyldibenzimidazoletetrasulfonate,

Anisotriazine,

Ethylhexyltriazone,

Diethylhexylbutamidotriazone,

Methylenebis(benzotriazolyl)tetramethylbutylphenol,

Drometrizole trisiloxane,

Polysilicone-15,

1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene,

2,4-Bis[5-1(dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine

and mixtures thereof.

The additional mineral screening agents are selected from among pigmentsor even nanopigments (mean size of the primary particles: generallybetween 5 nm and 100 nm and preferably between 10 nm and 50 nm) ofcoated or uncoated metal oxides such as, for example, nanopigments oftitanium oxide (amorphous or crystallized in rutile and/or anataseform), of iron oxide, of zinc oxide, of zirconium oxide or of ceriumoxide and mixtures thereof which are all UV photoprotective agents thatare well known per se. Standard coating agents are, moreover, aluminaand/or aluminum stearate. Such coated or uncoated metal oxidenanopigments are described in particular in EP-518,772 and EP-518,773.

The additional UV-screening agents in accordance with the invention aregenerally present in the compositions according to the invention inproportions ranging from 0.01% to 20% by weight relative to the totalweight of the composition, and preferably ranging from 0.1% to 10% byweight relative to the total weight of the composition.

The cosmetic compositions according to the invention may also containagents for artificially tanning and/or browning the skin (self-tanningagents) such as dihydroxyacetone (DHA). They are preferably present inamounts ranging from 0.1% to 10% and more preferably from 0.2% to 8% byweight relative to the total weight of the composition.

The compositions in accordance with the present invention may alsocomprise standard cosmetic adjuvants chosen especially from among fattysubstances, organic solvents, ionic or nonionic thickeners, softeners,humectants, antioxidants, moisturizers, desquamating agents,free-radical scavengers, antipollution agents, antibacterial agents,anti-inflammatory agents, depigmenting agents, propigmenting agents,opacifiers, stabilizers, emollients, silicones, antifoams, insectrepellents, fragrances, preservatives, anionic, cationic, nonionic,zwitterionic or amphoteric surfactants, substance P antagonists,substance CGRP antagonists, fillers, pigments, polymers, propellants,acidifying or basifying agents, or any other ingredient usually used incosmetics and/or dermatology.

The fatty substances may be an oil or a wax or mixtures thereof. Theterm “oil” means a compound that is liquid at room temperature. The term“wax” means a compound that is solid or substantially solid at roomtemperature, and whose melting point is generally above 35° C.

Oils that may be mentioned include mineral oils (paraffin); plant oils(sweet almond oil, macadamia oil, blackcurrant pip oil or jojoba oil);synthetic oils, for instance perhydrosqualene, fatty alcohols, fattyacids or fatty esters (for instance the C₁₂-C₁₅ alkyl benzoate soldunder the trademark “Finsolv TN” by Witco, octyl palmitate, isopropyllanolate, triglycerides, including capric/caprylic acid triglycerides,oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils(cyclomethicone and polydimethylsiloxanes or PDMS) or fluoro oils, andpolyalkylenes.

Waxy compounds that may be mentioned include paraffin, carnauba wax,beeswax and hydrogenated castor oil.

Among the organic solvents that may be mentioned are lower alcohols andpolyols. These lower polyols may be chosen from glycols and glycolethers, for instance ethylene glycol, propylene glycol, butylene glycol,dipropylene glycol or diethylene glycol.

The thickeners may be chosen especially from among crosslinked acrylicpolymers, for instance carbomers, acrylate/C₁₀-C₃₀ alkylacrylatecrosslinked polymers of the type such as Pemulen or polyacrylate-3 soldunder the name Viscophobe DB 1000 by Amerchol; polyacrylamides such asthe polyacrylamide, C₁₃-C₁₄ isoparaffin and laureth-7 emulsion soldunder the name Sepigel 305 by SEPPIC, AMPS homopolymers or copolymerssuch as Hostacerin AMPS sold by Clariant, modified or unmodified guargums and celluloses, such as hydroxypropyl guar gum,methylhydroxyethylcellulose and hydroxypropylmethylcellulose, xanthangum, and nanometric silicas of the Aerosil type.

Needless to say, one skilled in the art will take care to select theoptional additional compound(s) mentioned above and/or the amountsthereof such that the advantageous properties intrinsically associatedwith the compounds in accordance with the invention are not, or are notsubstantially, adversely affected by the envisaged addition(s).

The compositions according to the invention may be prepared according totechniques that are well known to those skilled in the art, inparticular those intended for the preparation of emulsions ofoil-in-water or water-in-oil type.

This composition may be in particular in the form of a simple or complexemulsion (O/W, W/O, O/W/O or W/O/W emulsion) such as a cream or a milk,in the form of a gel or a cream-gel, or in the form of a lotion, an oil,a powder or a solid tube, and may optionally be packaged as an aerosoland may be in the form of a mousse or a spray.

The compositions according to the invention are preferably in the formof an oil-in-water or water-in-oil emulsion.

When it is an emulsion, the aqueous phase of this emulsion may comprisea nonionic vesicular dispersion prepared according to known processes(Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965),FR-2,315,991 and FR-2,416,008).

When the cosmetic composition according to the invention is used to carefor the human epidermis, it may be in the form of a suspension or adispersion in solvents or fatty substances, in the form of a nonionicvesicular dispersion or in the form of an emulsion, preferably ofoil-in-water type, such as a cream or a milk, or in the form of anointment, a gel, a cream-gel, an antisun oil, a solid tube, a powder, anaerosol mousse or a spray.

When the cosmetic composition according to the invention is used forhaircare, it may be in the form of a shampoo, a lotion, a gel, anemulsion or a nonionic vesicular dispersion and may constitute, forexample, a rinse-out composition, to be applied before or aftershampooing, before or after dyeing or bleaching, or before, during orafter permanent-waving or relaxing the hair, a styling or treatinglotion or gel, a blow-drying or hairsetting lotion or gel, or acomposition for permanent-waving, relaxing, dyeing or bleaching thehair.

When the composition is used as a makeup product for the nails, thelips, the eyelashes, the eyebrows or the skin, such as an epidermaltreatment cream, a foundation, a tube of lipstick, an eyeshadow, amakeup rouge, a mascara or an eyeliner, it may be in solid or pasty,anhydrous or aqueous form, such as oil-in-water or water-in-oilemulsions, nonionic vesicular dispersions or suspensions.

The present invention also features formulation of at least one compoundof formula (1) into cosmetic compositions as an agent for controllingthe variation in the color of the skin caused by UV-A radiation.

This invention also features the use of at least one compound of formula(1) as defined above as an agent for photostabilizing synthetic polymerssuch as plastics or lenses, in particular spectacle lenses or contactlenses.

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative. Insaid examples to follow, all parts and percentages are given by weight,unless otherwise indicated.

EXAMPLE 1 Preparation of the di(trimethylsilanylmethyl) ester of3,3-diphenyl-2-propylidene)propanedioic acid

a) First Step: Preparation of trimethylsilanylmethyl malonate:

In a reactor fitted with a Dean-Stark apparatus malonic acid (20.7 g,0.199 mol) and hydroxymethyltrimethylsilane (41.4 g, 0.398 mol) in 150ml of toluene are refluxed for 4 hours in the presence of 0.5 ml ofconcentrated sulfuric acid. The water formed is removed azeotropically.The organic phase is washed twice with water, dried over sodium sulfateand concentrated under reduced pressure. Distillation under vacuum (b.p.90° C. under 0.02 hPa) gives 46.7 g (85% yield) oftrimethylsilanylmethyl malonate in the form of a colorless oil.

b) Second Step: Preparation of the Compound of Example 1:

In a reactor β-phenylcinnamaldehyde (5 g, 0.024 mol) is dissolved in 100ml of isopropanol. 0.6 ml of piperidine and trimethylsilanylmethylmalonate (7.1 g, 0.0258 mol) are added. The reaction mixture is heatedat 60° C. for 2 hours. The solution is concentrated under reducedpressure. The excess malonate is removed by distillation under a vacuumof 0.02 hPa. Purification by chromatography on a silica column (eluent:heptane, then 9:1 heptane/EtOAc) gives clean fractions of the derivativeof Example 1 (8.9 g, 80% yield) in the form of a thick liquid whichgradually crystallizes:

pale yellow solid

m.p. 50° C.

UV (ethanol) λ_(max)=333 nm, ε_(max)=28 610, E_(1%)=614.

EXAMPLE 2 Preparation of monotrimethylsilanylmethyl monoethyl diester of(3,3-diphenyl-2-propylidene)propanedioic acid (compound B)

a) First Step: Preparation of monotrimethylsilanylmethyl monoethylmalonate:

In a reactor a mixture of the potassium salt of monoethylmalonic acid(17 g, 0.1 mol) and chloromethyltrimethylsilane (12.2 g, 0.1 mol) in 50ml of DMF is heated at 70° C. for 24 hours. The reaction mixture ispoured into 100 ml of water and extracted with dichloromethane. Theorganic phase is washed twice with water, dried over sodium sulfate andconcentrated under reduced pressure. This gives 12 g of pale yellow oilcomposed of a mixture of monotrimethylsilanylmethyl monoethyl malonateand 2-(trimethylsilylmethyl)monotrimethylsilanylmethyl monoethylmalonate in a 4:1 ratio. This mixture is used as it is in the followingstep.

b) Second Step: Preparation of the Compound of Example 2:

In a reactor β-phenylcinnamaldehyde (5 g, 0.024 mol) is dissolved in 200ml of isopropanol. 0.6 ml of piperidine and the malonates mixture fromthe preceding step (8.5 g, 0.0255 mol of 2/a) are added. The reactionmixture is heated at reflux for 4 hours. The solvent is evaporated underreduced pressure. The oil obtained is taken up in dichloromethane andwashed with acidulated water. The organic phase is washed twice withwater, dried over sodium sulfate and concentrated under reducedpressure. The excess malonate and its impurity are removed by vacuumdistillation. The distillation residue is chromatographed on a silicacolumn (eluent: heptane, then 9:1 heptane/EtOAc) to give the compound ofExample 2 in the form of a colorless oil:

GC: 2 isomers are present, in a ratio of 50:50.

UV (ethanol) λ_(max)=334 nm, ε_(max)=28 270, E_(1%)=692.

EXAMPLE 3 Preparation of the monotrimethylsilanylmethyl ester of2-cyano-5,5-diphenyl-2,4-pentadienoic acid (compound F)

a) First Step: Preparation of trimethylsilanylmethyl cyanoacetate:

In a reactor fitted with a Dean-Stark apparatushydroxymethyltrimethylsilane (3.8 g, 0.036 mol) and cyanoacetic acid(3.1 g, 0.036 mol) in 50 ml of toluene are refluxed for 4 hours in thepresence of one drop of concentrated sulfuric acid. The organic phase iswashed twice with water and is dried over sodium sulfate. It isconcentrated under reduced pressure. Distillation under vacuum (b.p. 80°C. under 0.4 hPa) gives 4.3 g (69% yield) of trimethylsilanylmethylcyanoacetate in the form of a colorless liquid which is used as it is inthe following step.

b) Second Step: Preparation of the Compound of Example 3:

In a reactor β-phenylcinnamaldehyde (4.8 g, 0.023 mol) is dissolved in400 ml of isopropanol. 0.6 ml of piperidine and trimethylsilanylmethylcyanoacetate (4 g, 0.023 mol) are added. The reaction mixture is heatedat reflux for 2 hours. Water is added and the mixture is extracted withdichloromethane. The organic phase is washed with acidulated water andthen dried over sodium sulfate. The solvent is evaporated under reducedpressure . . . . This gives an oil which crystallizes. Recrystallizationfrom heptane gives 6.5 g (78% yield) of the derivative of Example 3 inthe form of pale yellow crystals:

m.p. 84° C.

UV (ethanol) λ_(max)=360 nm, ε_(max)=28 880, E_(1%)=800.

COMPOSITION EXAMPLE A

Concentration Phase Constituents (g %) A Glycerylmonostearate/polyethylene glycol 1 stearate (100 EO) mixture (Arlacel165 - Uniqema) Fatty acids of plant origin (Stearine TP 1.5 1200 -Stéarineries Dubois) Dimethicone (Dow Corning 200 Fluid 350 0.5 CS - DowCorning) Cetyl alcohol (Lanette 16 - Cognis) 0.5Cetylstearylglucoside/cetylstearyl alcohol 2 mixture (Montanov 68 -SEPPIC) C₁₂-C₁₅ alkyl benzoate (Finsolv TN - Witco) 10 Compound ofExample 1 5 B Glycerol (Pricerine 9091 - Uniqema) 5 Hexadecyl phosphate,potassium salts 1 (Amphisol K - Roche Vitamins) EDTA 0.1 C Xanthan gum(Keltrol T - CP Kelco) 0.2 Acrylates/C₁₀-C₃₀-alkylacrylate crosslinked0.2 copolymer (Pemulen TR-1 - Noveon) Isohexadecane (Isohexadecane - BP)1 Triethanolamine qs pH Preservatives qs Demineralized water qs 100 g

Manufacturing Protocol:

The fatty phase (A) is weighed out and heated on a water bath at 70° C.The aqueous phase (B) is weighed out in the final beaker and heated on awater bath at 70° C. The fatty phase is dispersed in the aqueous phasewith stirring using a Moritz rotor/stator stirrer (about 1000 rpm). Themixture of thickeners (C) is incorporated and the resulting mixture isallowed to cool to room temperature with stirring. At about 30° C., theformulation is neutralized and packaged.

Each patent, patent application, publication and literaturearticle/report cited or indicated herein is hereby expresslyincorporated by reference.

While the invention has been described in terms of various specific andpreferred embodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

1. A 4,4-diarylbutadiene-substituted methyltrialkylsilane having thestructural formula (1):

in which the radicals R₁, which may be identical or different, are eacha hydroxyl group, a saturated or unsaturated, linear or branched C₁-C₁₀alkyl radical, a linear or branched C₁-C₁₀ alkoxy radical, with theproviso that two adjacent groups R₁ may together form a C₁-C₃alkylenedioxy ring; the radicals R₂, R₃ and R₄, which may be identicalor different, are each a saturated or unsaturated, linear or branchedC₁-C₁₀ alkyl radical optionally containing one or more halogen atoms, ora phenyl radical; p is 0 or 1; A is a hydrogen atom, a saturated orunsaturated, linear or branched C₁-C₈ alkyl radical, a phenyl radical,or the group Si(CH₃)₃, with the proviso that, if A is Si(CH₃)₃, then p=0and R₂, R₃ and R₄ are methyl radicals; n is an integer ranging from 0 to2; W is a saturated or unsaturated, linear or branched C₁-C₈ alkyleneradical optionally substituted by a hydroxyl group; Z is a hydrogenatom, —(C═O)OR₅, —(C═O)R₆, —(C═O)NR₇R₈, —SO₂R₉, —CN or—(C═O)XCHA(W)_(p)SiR₂R₃R₄; the radical R₅ is a hydrogen atom, or asaturated or unsaturated, linear or branched C₁-C₂₀ alkyl radical; theradical R₆ is a linear or branched, optionally cyclic, C₁-C₂₀ alkylradical or a C₆-C₁₂ aryl radical; the radicals R₇ and R₈, which may beidentical or different, are each a hydrogen atom or a linear or branchedC₁-C₂₀ alkyl radicals; X is —O— or —NR₇—; and the radical R₉ is a linearor branched C₁-C₂₀ alkyl radical or a C₆-C₁₂ aryl radical, or mixturethereof.
 2. The 4,4-diarylbutadiene-substituted methyltrialkylsilane asdefined by claim 1, wherein formula (1), Z is a hydrogen atom.
 3. The4,4-diarylbutadiene-substituted methyltrialkylsilane as defined by claim1, wherein formula (1), Z is —(C═O)OR₅.
 4. The4,4-diarylbutadiene-substituted methyltrialkylsilane as defined by claim1, wherein formula (1), Z is —(C═O)R₆.
 5. The4,4-diarylbutadiene-substituted methyltrialkylsilane as defined by claim1, wherein formula (1), Z is —(C═O)NR₇R₈.
 6. The4,4-diarylbutadiene-substituted methyltrialkylsilane as defined by claim1, wherein formula (1), Z is —SO₂R₉.
 7. The4,4-diarylbutadiene-substituted methyltrialkylsilane as defined by claim1, wherein formula (1), Z is —CN.
 8. The 4,4-diarylbutadiene-substitutedmethyltrialkylsilane as defined by claim 1, wherein formula (1), Z is—(C═O)XCHA(W)_(p)SiR₂R₃R₄.
 9. The 4,4-diarylbutadiene-substitutedmethyltrialkylsilane as defined by claim 1, wherein formula (1), X is—O—.
 10. The 4,4-diarylbutadiene-substituted methyltrialkylsilane asdefined by claim 1, wherein formula (1), X is —NR₇—.
 11. The4,4-diarylbutadiene-substituted methyltrialkylsilane as defined by claim1, wherein formula (1): Z=—(C═O)OR₅, —CN or (C═O)XCHA(W)_(p)SiR₂R₃R₄; R₅is methyl or ethyl; A is H; R₂ to R₄ are C₁-C₄ alkyl radicals; n is 0; pis 0 or 1; and W is a C₁-C₂ alkylene radical.
 12. The4,4-diarylbutadiene-substituted methyltrialkylsilane as defined by claim1, having the structural formula of compound (A):


13. The 4,4-diarylbutadiene-substituted methyltrialkylsilane as definedby claim 1, having the structural formula of compound (B):


14. The 4,4-diarylbutadiene-substituted methyltrialkylsilane as definedby claim 1, having the structural formula of compound (C):


15. The 4,4-diarylbutadiene-substituted methyltrialkylsilane as definedby claim 7, wherein formula (1): A is H; R₂ to R₄ are C₁-C₄ alkylradicals; n is 0; p is 0 or 1; and W is a C₁-C₂ alkylene radical. 16.The 4,4-diarylbutadiene-substituted methyltrialkylsilane as defined byclaim 1, having the structural formula of compound (D):


17. The 4,4-diarylbutadiene-substituted methyltrialkylsilane as definedby claim 1, having the structural formula of compound (E):


18. The 4,4-diarylbutadiene-substituted methyltrialkylsilane as definedby claim 1, having the structural formula of compound (F):


19. The 4,4-diarylbutadiene-substituted methyltrialkylsilane as definedby claim 1, having the structural formula of compound (G):

20-35. (canceled)